Phthalocyanine azo dyes on cellulosic fibers



diazotized di-,

1 and alkoxy,

' groups.

Patented Jan. 18, 1944 PHTHALOGYANINE AZO DYES N CELLULOSIC FIBERS Harold Blackshaw Blackle'y, Manchester, Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application May 22, 1942, Serial No.

444,107; In Great and Norman Hulton Haddock,

England, assignors to Britain September 25, 1939 8 Claims. .(Cl. 8-46) The present invention relates to the coloring of cellulosic fiber, this application being a con tinuation-in-part from our copending application Serial No. 355,692, filed September 6, 1940. More particularly this application relates to dyeing or printing of cellulosic fiber by impregnating-the same with a diazotized poly-aminophthalocyanine' compound, and subsequently submitting the impregnated fiber to an aftertreatment as hereinafter described, to develop a water-insoluble azo dye on the fiber.

This invention is basedon the discovery that triand tetra-amino-phthalocyanines have aifinity for cellulosic fibers, which they dye in the same wayas, for example, diazo dyestuffs derived from benzidine, and that by treating the cellulosic fibers with the said-diazotized poly-amino-phthalocyanines, in the manners described below, brown and violet to green and grey 'shades of good fastness properties are obtained thereon,

When we speak or diazotized poly-aminophthalocyanines, we are referring to compounds obtainable by treating di-, trior tetra-aminophthalocyanines, for instance tetra-amino-copper-phthalocyanine, tetra-amino-cobalt-phthalocyanine, tetra-amino-metal-free-phthalooyanme, or their homologs, analogs and nuclear substitution derivatives, such as chloro, nitro alkyl with various quantities of nitrous acid, to diazotize at least some-oi the amino The preferred procedure-is to use suflicient nitrous acid to diazotize theoretically all the amino groups present in the molecule. But even here there is no certainty as to the number of diazonium groups in the final compound, because the resulting compound is generally not stable and may undergo partial decomposition before it has a chance to be applied to the fiber.

The aftertreatment is carried out by treating the cellulosic fiber, which has been impregnated with the diazotized poly-amino-phthalocyanine, with azo-dye coupling components which are free of sulfo, 'carboxy or similar water-solubilizing groups. Principal consideration among these deserve the azoic, or so-called ice-color, coupling components. These are typified by p-naphthol, 2-hydroxy-3-naphthoic anilide, bis-acetoacet-o- .tolidide, 1-phenyl-3-methyl-5-pyrazolone," resorcinol, a-naphthol, 2 3-hydroxy-naphthoic-otoluidide, 2:3-hydroxynaphthoic-p-anisidide and the p-chloranilide of 2-hydroxycarbazole-3-carboxylic acid.

' As equivalents coming within the scope of this invention may be mentioned other coupling components free of water-solubilizing groups, such as phenol, p-cresol, aceto-acetic ester, and acetoacet-p-phenetidide, as well as coupling components which per 'se are soluble but can be converted into water insoluble compounds on the fiber by lactamization. See, for instance, U. S. Patents Nos. 2,012,994; 2,012,991 and 2,098,276.

The said coupling component may be applied to the fiber which hasbeen dyed or printed with e the phthalocya'nine diazo compound, in any convenient manner. The coupling components are then applied from solutions prepared in the usual manner, for instance by the aid of alkali, as is customary in carrying out azoic couplings.

Inv reaction with the coupling components the diazotized aminophthalocyanines are presumed to yield primary azo dyestufis, in which'it is understood that/ the diazonium nitrogen atoms remain intact.

Accordingly, the present invention relates to a process for dyeing or printing cellulosic fiber, which comprises impregnating the fiber with a solution or printing paste containing a diazotized poly-amino compound of the phthalocyanine series, and subsequently treating the impregnated fiber in such a manner as to develop a waterinsoluble azo dye on the fiber. In this way, ac-

there are obtained on cellulosic fibers brown or violet to green and grey shades of good fastness properties, including fastness to washing.

For dyeing, the cellulosic fiber, e. g. cotton or regenerated cellulose, is conveniently treated with the diazotized poly-amino-phthalocyanine by immersing it at'0-30 C. in an aqueous solution of the latter. The diazotized tetra-aminophthalocyaninesusable as starting materials are described in copending application of Haddock, Serial No. 335,871 (Patent No. 2,280,072, issued April ess set out therein. The corresponding compounds of lesser diazo content may be prepared by reducing and diazotizing in similar manner the dinitro and trinitro-phthalocyanines described in-British Patent No. 541,146 (p. 2, lines 104-111; p. 4, lines 68-78).'

Taking the tetra-amino-phthalocyanine of copper as typical,-the same may be diazotized ready for use, or there may be employed acidified solutions ofthe metallic double salts of the diazotized tetra-amino-phthalooyanine, or the corresponding alkali-metal isodiazotates. Metallic tetra-amino-phthalocyanines other than those of copper may be used for preparing diazo com- 21, 1942), and may be obtained by the procpoundsfsuitable' for use in the ines can also be used.

' Copper-tetra-(4) -amino v process of the invention; for example, those of magnesium, cobalt, nickel, lead or aluminium, which are conveniently prepared by heating the appropriate metal or metal salt'with a nitrophthalonitrile and reducing the resulting tetra-nitrophthalo- MetaL-free not limited by the parts are The invention is illustrated but the following examples in which by weight.

. Example 1 To' a stirred suspension of 2 parts of copper tetra-(4) -amino-phthalocyanine in 40 parts of 50 parts of 33% aqueous hydrochloric acid, at 5 0., there is rapidly added a solution of 1 part of sodium nitrite dissolved in 20 parts oLwater. The dark-green solutionso obtained is filtered and diluted to 1400 parts with equal quantities of ice and water. i. r

Into 350 parts of the diazonium solution thus of p-naphthol dissolved in 250 parts of 0.1% sodium hydroxide solution at is then taken out, rinsed in cold-water and dried. A violet shade of excellent fastness to washing is produced.

Instead of fl-naphthol there may be employed 2-hydroxy-3-naphthoic anilide. By this means -a similar violet shade of similar fastness properties is obtained.

Other violet shades are obtained by employing .2z3-hydroxynaphthoic o-toluidide or v2:3-hychloranilide of 2-hydroxycarbazole-3-carboxylic acid a grey shade is produced.

Similar. shades are also obtained by using tetra-diazotized cobalt or nickel tetra- (4) -amino-phthalocyanine in place of tetradiazotized copper-tetra-(4) -amino-phthalo-cyanine.

Example 2 parts of cotton yarn are impregnated with diazo compound as in Example 1 and are then introduced into a solution of 0.5 part of bisacetoacet-o-tolidide in 250 parts of 0.1% sodium o-tolidide an olive-green shade is produced, having. good fastness to washing. If .1-phenyl-3- methyl-s-pyrazolone I acetoacet-o-tolidide, a yellowish-green shade of good fastness to washing is produced.

Example 3 phthalocyanine is d as in Example --1 and filtered. Cotton cloth is padded with the undiluted filtrate in such a way as to leave an amount of the diazo solution equal in weight to the weight of the dry cloth in the fiber. Coupling of the diazo on azotize tetra-amino-phthalocyantized as in Example 1, and filtered.

' um chloride (obtained as described etidide or phenyl-methyl-pyrazolone isv employed. ,With ,8hydroxy-naphthoic anilide, a

dull violet dyeing is obtained. In ings with very good washing light fastness are obtained.

Example 4 v Copper tetra- (H-amino phthalocyanine is amall cases, dyefastness and good to a printing paste by the addition .of a thickener, as for-example gum tragacanth. Cotton cloth is printed with this paste. Coupling with beta-hydroxy-naphthoic-anilide is effected by turning the printed fabric in a solution concoupling component per liter of water and sumcient sodium'hydroxide to maintain Clayton Yellow alkalinity, the temperature being. maintained at approximately 5 C. The cloth is. then. rinsed in cold water, soaped, rinsed again, and dried. There results a print 01' dull violet shade, which displays excellent wash- .ing iastness and good light fastness.

. Cotton cloth .is printed with a printing paste consisting of the potassium isodiazotate derived from copper phthalocyanine tetra-(4) -diazoni below), hisactoacet-o-tolidide, neutral starch-tragacanth thickening, Turkey red oil and water.- After steaming. for ten minutes, soaping, rinsing and drying, abright green print is obtained which has very good wash fastness and good light fastness.-

The potassium tetra-(4) -iso-diazotate of copper phthalocyanine hereinabove mentioned may be made as follows:

parts of finely divided copper tetra-(4) amino-phthalocyanine in the form of anaqueous is usedin place of bispaste are mixed with 350 parts of water and 150 parts of concentrated aqueous hydrochloric acid To the mixture at 5 Cris added a solution of 15 parts of sodium nitrite in 50 parts of water. The temperature is maintained throughout at 5 C. or below. The dark green diazo solution is nowadded to a stirred mixture 510" C. of 1200 parts of potassium hydroxide and 800 parts of water. obtained is added rapidly to a mixture of 1600 parts of potassium hydroxide and 400 parts of water previously heated to 120. The temperature is maintained at not less than 120 C. during the addition. The mixture is cooled to 100 C. and the tetra-isodiazotate, in suspension, is filtered off through asbestos paper. It is pressed under vacuum till dr The product is a dark green powder soluble in cold water to give a bluish green solutio the fiber to phenol is carried out by stirring the In most of the examples-above, tion of tetra-amino copper phthalocyanine has been indicated as freshly prepared and used immediately, in view of its tendency to decompose on standing. If desired, instead of the free diazonium compound, acidsolutions of its double salts,

with inorgamc compounds. chloride, or its compounds with aromatic sulfonic acids, for instance, l,5-naphthylene-disulfonic acid, may be used. (See U. S. Patent No. 2,280,072); We have found, incidentally, that a considerable degree of stabilization may be achieved by adding surface-active quaternary The green solution sothe diazo soluammonium compounds, such as long-chain-alkylpyridinium-halides. Thus we have found that the addition to the dye bath of 0.25% of cetyl-pyridinium bromide in the presence of free hydro-- Y chloric acid would stabilize the tetradiazonium derivative of tetra-(4) -amino-copper-phthalocyanine to such an extent that after 2 hours at 17 0., the amount of decomposition found was slight.

In lieu of the tetradiazo compound obtained from copper-tetra (4) amino phthalocyanine employed in the above examples, there may be used with equal success the tetra-diazo-compound from copper-tetra- (3) -amino-phthalocyanine, the tridiazo compound obtained from copper-tri- (4) or tri-(B) amino phthalocyanine,

the bis-diazo compound from copper-diamino- -phthalocyanine, also the corresponding diazon-- ium compounds derived from cobalt and nickel with an azo coupling'component devoid of sulfo and carboxy groups.

3. A process for dyeing cellulosic fiber, which comprises impregnating the same with a solution of a polydiazonium compound obtained by diazotizing a tetra-amino-compound of the phthalocy- I anine series, and then treating the impregnated fiber with a solution of an azoic coupling component to produce a water-insoluble dyestufi! on the fiber.

4;. A process for dyeing cellulosic fiber, which comprises impregnating the same with an aqueous solution of a polydiazonium compound obtained tetra-amino and tri-amino-phthalocyanines, and

the diazonium compounds derived from tetraamino and tri-amino metal-free phthalocyanines.

The dyeings obtained on cellulosic material according to this invention are all characterized by good fastness towashing, soap boiling, open soda bo n and light.

It will be understood that the detailed practice of our invention is susceptible to wide variation by diazotizing a tetra-amino-copper-phthalocyanine, and then treating the impregnated fiber with a solution of an arylide of aceto-acetic acid.

5. A process for dyeing cellulosic fiber which comprises impregnating the same with tetradlazotized copper-tetra -(4) -amino phthalocyanine, and then treating the impregnated fiber with a solution of an azoic coupling component selected from the group consisting of oz and p-naphand modification within the skill of those-engaged in this art. a

We claim:

1. A process for coloring cellulosic fiber, which comprises impregnating the same with a polydiazonium compound obtained'by diazotizing a polyamine of the phthalocyanine series, and then subjecting the impregnated fiber to treatment with a coupling component adapted to develop a water-insoluble azo dye on the fiber.

2. A process for coloring cellulosic fiber,which comprises impregnating the same with a polydiazonium compound obtained by diazotizing a polyamine of the phthalocyanine series, and then subjecting the impre; dated fiber to treatment 8. A process for dyeing cellulosic fiber, which comprises impregnating the fiber with an aqueous solution of the poly-diazonium compound obtained by diazotizing tetra-amino-copper phthalocyanine, and then treating the impregnated fiber with an azoic coupling component to produce a water-insoluble poly-azo dyestuff on the fiber.

HAROLD BLACKSHAW. NORMAN HUL'I'ON HADDOCK. 

